The paper presents an investigation into the durability of functionalized carbon structures (FCS) in a highly alkaline concrete environment. First, the suitability of optical fibers with different coatings-i.e., acrylate, polyimide, or carbon-for the FCS was investigated by subjecting fibers with different coatings to micro/macro bending and a 5% sodium hydroxide (NaOH) (pH 14) solution. Then, the complete FCS was also subjected to a 5% NaOH solution. Finally, the effects of spatial variation of the fiber embedded in the FCS and the bonding strength between the fiber and FCS was evaluated using different configurations -i.e., fiber integrated into FCS in a straight line and/or with offsets. All three coatings passed the micro/macro bending tests and show degradation after alkaline exposure, with the carbon coating showing least degradation. The FCS showed relative stability after exposure to 5% NaOH. The optimum bonding length between the optical fiber and the carbon filament was found to be ≥ 150 mm for adequate sensitivity.